NaNH<sub>2</sub> as a Nitrogen Source and Base to\nSynthesize Triarylamines from Aryl Halides Using Pd-Catalyzed C–N\nCoupling

Triarylamines (TAAs) are excellent core structures for\nmultifunctional\nmaterials. Reversible single-electron oxidation is the key to versatile\napplications. Synthesizing these from feedstock materials is inevitable.\nHere, we report the one-pot synthesis of TAAs from aryl halides and\ninexpensive NaNH<sub>2</sub> as a nitrogen source and base (dual role).\nThe Pd/Xantphos catalytic system shows excellent selectivity toward\nTAAs from aryl bromides without adding organic amines and an additional\nbase. Various <i>para</i> substituents on the aryl ring\nshow good functional group tolerance in the presence of NaNH<sub>2</sub>, resulting in moderate to excellent yield (20–91%). Even\nthough the <i>meta</i>-substituted aryl bromides give TAA\nproducts in moderate to excellent yields (20–81%), the <i>ortho</i> substitution leads to only diarylamine products. TAAs\nfrom aryl chlorides can be achieved only by changing the ligand to\nXphos. The mechanistic investigation suggests that three sequential\nC–N cross-coupling reactions give the TAA products in the presence\nof NaNH<sub>2</sub>. The photophysical and electrochemical properties\nof TAAs and corresponding radicals were tunable based on substitution\npatterns.